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DETERMINATION  OF  THE  LATENT  HEATS  OF  VAPORIZATION 
OF  A FEW  COMMERCIAL  FATTY  ACIDS 


BY 


ALEXANDER  WATT  THOMSON  LOVELESS 


THESIS 


FOR  THE 


DEGREE  OF  BACHELOR  OF  SCIENCE 


IN 


CHEMICAL  ENGINEERING 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 


UNIVERSITY  OF  ILLINOIS 


1922 


* 


Ai 

X 


UNIVERSITY  OF  ILLINOIS 


c 

i£ 


_A.ngns.t_  -12 1 922 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 



ENTITLED.  -THE-  JDETERMXU  AT  IDN_  JDF-  -THE-  -LATENT.  - HEAHS  - -OF-  - VAP-OS  IZA^D-I-O-N-  - 

DP-  -A.  -PKl-  _C  QMMEEDIAL  _ P.M1IY.  -AC-IBS 

IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF  _ _B  AGHELQB- _QF_ -SDIEN DE 


Instructor  in  Charge 


Approved 


O HEAD  OF  DEPARTMENT  OF 


ftlLl  ' 


Py-4  ^4  n^> 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/determinationoflOOIove 


. . . 

...  J 


TABLE  OF  CONTENTS 


Page 

I.  INTRODUCTION  1 

II.  REVIEW  OF  LITERATURE  2 

Previous  Determination 

Methods.  .......  ............... 

III.  EXPERIMENTAL 5 

Calorimetric  Method.  ....  

Vapor  Pressure  Method 

IV.  TABULATED  DATA 

Tabulated  Results . 23 

V.  SUMMARY 24 

VI.  BIBLIOGRAPHY . 25 


]lj 


1 

THE  DETERMINATION  OF  THE  LATENT  HEATS  OF  VAPORIZATION  OF 
A FEW  COMMERCIAL  FATTY  ACIDS. 

I.  INTRODUCTION. 

Most  of  the  fatty  acids  dealt  with  in  this  Investigation  are 
used  industrially  in  the  manufacture  of  laundry  soaps  and  washing 
powders.  With  the  exception  of  the  stearic  and  oleic  acids  the 
stock  was  obtained  from  low  grade  greases  and  foots.  The  crude 
vegetable  oils  consist  principally  of  a mixture  of  the  glycerides  of 
palmitic,  linoleic  and  oleic  acids  with  varying  amounts  of  the  gly- 
cerides of  arachidie  and  stearic  acids.  In  addition  to  these  gly- 
cerides there  are  also  present  the  glycerides  of  all  these  acids  in 
various  stages  of  decomposition. 

Crude  cottonseed  oil  for  example  is  usually  refined  with  caustic 
soda,  whereby  the  partially  and  wholly  decomposed,  glycerides  are 
separated  out  as  a soap  technically  known  as  foots.  This  soap  is 
only  partially  saponified  and  contains  considerable  quantities  of 
neutral  oil,  together  with  most  of  the  coloring,  nitrogenous  and 
mucilaginous  matter  that  was  present  in  the  crude  oil.  The  composi- 
tion of  the  foots  will  vary  considerably,  depending  to  a great  ex- 
tent upon  the  source  and  upon  the  amount  of  neutral  oil  retained  in 
refining. 

The  foots  may  be  "killed”  and  acidulated,  i.e.,  the  saponifica- 
tion may  be  completed  by  boiling  with  sufficient  alkali  and  the  re- 
sulting soap  treated  with  mineral  acid  to  liberate  the  fatty  acids. 


• • 


r 


; 


.■ 


. . . 


2 


Another  method  may  be  used  in  which  the  foots  may  be  first  treated 
with  a mineral  acid  to  free  it  from  alkali,  and  then  saponified  by 
the  Twitchell  or  other  process  to  split  off  the  remaining  glyceryl 
radicals.  In  either  case  the  resulting  product  is  a mixture  of 
free  fatty  acids,  which  must  be  steam  distilled  to  remove  the  ob- 
jectionable coloring  matter  before  they  can  be  utilized  in  the  manu- 
facture of  soap. 

In  the  design,  development,  and  calculation  of  costs  of  opera- 
tion of  these  distillation  plants  one  of  the  important  factors  is 
the  latent  heat  of  vaporization  of  these  fatty  acids. 

II.  REVIEW  OP  LITERATURE. 

A search  of  the  literature  gave  a great  deal  of  information  con- 
cerning the  methods  for  the  determination  of  the  latent  heats  of 
vaporization  of  simple  substances  that  boiled,  under  atmospheric  pres- 
sure without  decomposition.  The  only  article  on  the  substances  in 
question  was  written  by  Julius  Alsberg1  when  engaged  in  development 
work  along  the  lines  of  fatty  acid  distillation. 

He  suggested  that  the  heat  of  vaporization  could  be  calculated 
from  the  vapor  pressure  curves  of  the  fatty  acids  but  preferred  to 
determine  a heat  balance  of  a distillation  plant  which  was  available. 
Two  distillations  were  run  on  entirely  different  lots  of  fatty  acids 
and  several  months  allowed  to  elapse  between  runs.  The  distillation 
plant  was  operated  on  fresh  fatty  acid  stock,  with  no  fatty  acid  or 
pitch  left  in  the  still  from  previous  distillations.  Before  start- 
ing the  tests  distillation  was  carried  on  until  conditions  were  con- 


i . o'  • 


' 


r 


. ' . t 


■ 


3 


stant.  A flying  start  and  stop  of  the  tests  were  used  in  a manner 
similar  to  that  employed  in  making  evaporative  boiler  tests*  Thus 
without  interruption  or  disturbance  of  the  distillation,  tests  were 
started  and  stopped  immediately  after  emptying  the  condenser  drums* 
The  plant  consisted  of  a coal  fired  still,  supplied  with  superheated 
steam  through  a reducing  valve  and  a separately  fired  superheater* 
This  still  was  fed  continuously  so  that  the  volume  in  the  still  was 
constant,  the  level  in  the  gauge  glass  being  carefully  watched.  The 
combined  fatty  acid  vapor  and  superheated  steam  passed  over  from  the 
still  to  a water  cooled  tubular  type  condenser.  Here  the  fatty  acids 
were  condensed  and  collected  in  a drum  at  the  bottom  of  the  condenser 
The  distilled  fatty  acids  were  allowed  to  stand  until  laboratory 
tests  showed  that  all  the  moisture  had  settled  out. 

The  steam  passed  over  to  a barometric  condenser,  and  the  fixed 
gases  were  taken  care  of  by  a vacuum  pump.  The  barometric  condenser 
discharged  into  a separatory  catch  basin,  where  the  small  quantity 
of  entrained  fatty  acid  was  recovered  by  skimming. 

The  cooling  water  w as  carefully  weighed,  allowance  being  made 
for  surface  evaporation  from  the  top  of  the  open  condenser  and  scale 
tanks.  This  allowance  was  based  on  actual  loss  in  evaporation  of 
an  open  vessel  immersed  in  the  top  of  the  condenser. 

The  quantity  of  steam  was  determined  by  a specially  calibrated 
Gebhardt  steam  flow  meter  located  between  the  reducing  valve  and 
the  superheater. 

From  the  tabulated  data  Alsberg  struck  a heat  balance.  In  this 


4 


balance  it  was  assumed  that  the  steam  as  measured  was  dry  and  satu- 


rated. An  error  of  perhaps  one -half  of  one  per  cent  enters  here. 
It  was  further  assumed  that  there  was  practically  no  condensation 
in  the  vapor  pipe  connecting  the  still  with  the  condenser. 


Total  heat  above 
32°F  in  the  fatty  = 
acid  distilled. 


+ 


+ 


+ 


Heat  Balance 


(Heat  taken  up  by) 
(condensing  water) 


(Heat  lost  by  ra-) 
(diation  from  con) 
(denser  shell  ) 

(Total  heat  above) 

( 32°F  of  steam  ) 
(leaving  conden-  ) + 

( ser  ) 

(Heat  to  raise  ) 
(stock  ig  dnum  ) 
(from  32  F to  ) + 

(drum  temperature) 


(Heat  lost  by  evapo-) 
+ (ration  of  conden-  ) 
(sing  water  ) 

Total  heat  above  32°  B' 
of  steam  entering 
condenser 

o 

(Heat  above  32  F in  ) 
(water  carried  over  ) 
(with  stock  into  ) 
(settling  tank  ) 

(Heat  to  raise  stock) 
(from  cajch  basin  ) 
(from  32  F to  con-  ) 
(denser  temperature  ) 


Alsberg  then  gives 

the  following  values 

for  cottonseed  oil  fatty 

acids . 

130.5 

B.t .u./ 

lb 

at  24.51 

inch  vacuum 

118.0 

B.t.u./lt) 

at  25.14 

inch  vacuum 

Alsberg  accounts  for  the  discrepancy  by  the  difference  in  the 
stock  used  for  the  two  determinations,  and  by  the  fact  that  the 
tests  were  made  at  different  pressures  and  temperatures. 


Alsberg  admits  a discrepancy  of  9 per  cent  whereas  the  actual 
discrepancy  is  nearer  11  per  cent  as  calculated  from  his  figures. 
The  actual  pressures  within  the  apparatus  in  each  case  were  4.45 


\ 


; • ; • 


f 


' ; 


■ 


. 


i • 


• ■ ■ • i 


5 


inches  and  4.59  inches  of  mercury.  This  difference  is  too  small  to 
account  for  an  11  per  cent  difference  in  results. 

III.  EXPERIMENTAL. 

It  was  decided  to  make  calorimetric  de terminations  on  several 
commercial  samples  and  later  to  attempt  to  check  these  values  from 
the  vapor  pressure  curves  of  the  fatty  acids  by  means  of  the 
Clausius-Clapeyron  equation. 

One  of  the  most  serious  causes  of  error  in  all  calorimetric 
work  is  the  more  or  less  uncertain  correction  for  cooling#  This 
was  obviated  by  the  use  of  a modified  form  of  a Parr  Adiabatic 
Calorimeter. 

The  still  used  in  conjunction  with  the  adiabatic  calorimeter 
was  similar  to  a modified  form  of  Kahlenberg's  apparatus  that  was 
used  by  T.  W.  Richards  and  J.  H.  Mathews2  in  their  redeterraination 
of  the  heat  of  vaporization  of  water.  (Figure  I) 

The  boiling  liquid  was  surrounded  by  a vacuum  jacket  whose  walls 
were  about  one  centimeter  from  the  walls  of  the  boiling  compartment 
save  at  the  bottom  where  the  space  was  five  millimeters  across.  In 
addition  to  a hood  covering  the  upper  end  of  the  vapor  delivery 
tube,  the  tube  was  also  provided  with  another  trap  to  catch  and  re- 
tain any  liquid  that  might  in  any  way  gain  access  thereto.  This 
distance  between  it  and  the  condenser  might  be  reduced  to  a minimum, 
yet  it  was  surrounded  by  the  boiling  liquid  in  order  to  prevent  con- 
densation v/ithin  it.  The  heating  coil  was  placed  so  low  as  to  make 


6 

sure  that  the  liquid  surrounding  the  trap  was  at  the  boiling  point. 
The  interior  of  the  vacuum  jacket  was  brightly  silvered  to  a height 
of  4 or  5 centimeters,  the  silvering  being  on  both  walls,  so  that 
the  heat  passing  from  the  boiling  liquid  to  the  calorimeter  water 
by  radiation  had  to  pass  through  two  brightly  silvered  surfaces  and 
a vacuum  space.  The  conduction  of  heat  to  the  calorimeter  through 
the  glass  itself  cannot  be  prevented,  but  was  made  small  by  having 
the  glass  as  light  as  was  consistent  with  the  strength  demanded. 

The  apparatus  that  was  tried  for  the  distillation  of  the  fatty 
acids  was  practically  a duplication  of  Richards  apparatus  with  the 
following  two  exceptions.  A jacket  filled  with  cottonseed  oil  was 
placed  between  the  Dewar  jacket  and  the  boiling  compartment.  The 
heating  element  was  placed  in  this  oil  bath  because  it  was  thought 
that  local  heating  of  the  fatty  acids  in  immediate  contact  with  the 
wire  would  cause  considerable  decomposition. 

The  objection  to  this  apparatus  was  that  in  spite  of  all  pre- 
cautions bumping  was  so  violent  that  some  liquid  was  unquestionably 
carried  over.  The  acids  worked  with  were  mixtures  of  constituents 

o 

whose  boiling  points  varied  over  30  C.  The  lighter  fractions  would 
distill  early.  The  heavier  fractions  that  were  spattered  on  the 
hot  walls  of  the  oil  bath  vaporized  and  later  condensed  in  the  de- 
livery tube.  This  made  a calorimetric  determination  out  of  the 
question  for  the  length  of  time  available. 

The  Clausius-Clapeyron  relation  may  be  written  in  various  forms 
the  more  common  being 


6a 


A 

B 

C 

c' 

D. 

E 

E 

G. 


LEGE ED 

S/ bye  reef  surface 
Si /(erect  sucfuce 
Vapor  trap 
Vapor  trap 
Det/yerp  tube 

E/ectr/ca/Zp  ZeatecZ  o/Z pacZet 


Water  }/ne 

DeZ/rerp  tube  to  cor? (Leaser 
tin  t/re  apparatus  mac/e  of" 
Eprep  Er/ass. 


T 

1 

P 

J 


dP 

dT 


P (v"  - v* ) T dp 
J P dT 

absolute  temperature  at  boiling  point, 
latent  heat  of  vaporization  per  unit  weight, 
absolute  pressure. 

Joules  mechanical  equivalent  of  heat, 
specific  volume  of  vapor, 
specific  volume  of  liquid. 

the  temperature  rate  of  change  of  pressure  or 
the  slope  of  the  vapor  pressure  curve. 


For  all  practical  purposes  v'  is  so  small  as  compared  to  v" 
that  it  may  be  neglected  without  a serious  error.  In  this  form  it 
is  necessary  to  determine  the  specific  volume  of  the  vapor  at  the 
pressure  in  question. 

At  this  time  W.  K.  Lewis  and  H.  G.  Weber3  published  a method  of 
estimating  the  vapor  pressure  of  a liquid  at  any  temperature,  one 
point  on  whose  vapor  pressure  curve  is  known,  and  a method  of  getting 
heats  of  vaporization  from  vapor  pressure  data  by  a consideration 
of  the  Clausius  equation. 

At  reduced  pressures  vapors  may  be  considered  to  obey  the  gas 
laws  and  the  Clausius  equation  applied  to  vaporization  of  a liquid 
may  be  written: 


(1) 


dP 

PdT 

L 

R 


RT2  in  which 

molal  heat  of  vaporization 

the  gas  constant 


8 

The  vapor  pressure  curves  of  all  liquids  possess  great  curva- 
ture; consequently  where  only  a few  points  on  a curve  are  known  it 
is  very  difficult  to  interpolate  either  mathematically  or  graphically 
with  accuracy.  On  the  other  hand  the  vapor  pressure  curves  of  all 
liquids  are  more  or  less  parallel  and  it  is  a fact  that  if  instead 
of  plotting  the  vapor  pressure  of  a liquid  at  a given  temperature 
one  will  plot  against  the  temperature,  the  temperature  at  which  some 
liquid  of  reference,  e.g.,  water,  exerts  the  same  pressure,  one  will 
obtain  a curve  which  is  very  flat,  often  sufficiently  so  to  be  con- 
sidered a straight  line  over  a wide  range  of  temperature.  This  fact 
was  first  developed  by  J.  Johnston". 

The  Clapeyron  relation  as  applied  to  the  liquid  of  reference  is: 

( 2 ) dPw  = Lw 

PwdTw  RTws 

The  method  of  plotting  Tv/  against  T, given  above  is  equivalent 
to  placing  P = Pw,  when  also  dP  = dPw. 

Dividing  equation  (1)  by  equation  (2)  we  obtain 

(3)  dTw  = _L  (Tw)2 

dT  Lw  (T  ) 

The  left  hand  hand  side  of  equation  (3)  is  the  slope  of  the 

Tw  - T plot  mentioned  above.  Since  the  curve  is  substantially  a 

straight  line  the  slope  may  be  written  A Tw,  i.e.  finite  temper a- 

AT 

ture  differences  may  be  employed  in  calculation. 


9 


Water  was  used  as  the  reference  substance  because  steam  tables 
were  available.  Two  boiling  points  at  two  different  pressures  were 
obtained  and  the  values  substituted,  in  the  above  equation. 

The  apparatus  used  to  determine  the  vapor  pressure  of  the  fatty 
acids  was  set  up  as  illustrated  in  Figure  2.  A charge  of  the  sample 
was  placed  in  the  still  A and  the  cottonseed  oil  bath  heated  by 
means  of  a Bunsen  burner.  The  pressure  regulator  F was  partially 
filled  with  mercury,  the  entire  apparatus  closed  and  the  vacuum  pump 
started.  The  weight  of  mercury  in  the  tube  F kept  the  valves  G 
closed  until  the  difference  in  pressure  between  that  of  the  atmos- 
phere and  that  within  the  apparatus  was  sufficient  to  lift  the  valve. 
Adjustments  of  pressure  were  made  by  varying  the  amount  of  mercury 
in  the  regulator.  The  fatty  acid  were  raised  to  the  boiling  point 
and  refluxed  until  the  thermometer  read.ings  were  fairly  constant. 

A series  of  ten  readings  of  temperature  and  pressure  were  then  re- 
corded at  one  minute  intervals.  The  average  of  these  was  assumed  to 
be  the  boiling  point  of  the  sample.  The  pressure  regulator  was  suf- 
ficiently sensitive  to  maintain  the  pressure  within  one  millimeter 
providing  all  joints  were  tight. 


' • 


' • 

* 


' 

• 

« 

- 

. 

. 

. 

• * 

- 

• 

• 

• 

« 

10 


O/ayrammat/c  sketch  of  apparatus  s/sec/  /n  tAe 
determination  of  the  vapor  / ressare  of  fatty  acids. 

A ~ Pyrex.  ct/st/i/iny  ftask, 

3~  ftermo  meter  y rad  a a ted  to  read  to  tenths  of  a deyree , 

C.  ~ Pef/u X condenser . 

Dr  Merco/ry  manometer 

E.  ~~  Three  t/ter  f/ask  l/sed  to  ass/st  /n  yoressane  reya/at/on. 
p—  AAerco/ny  f '//ed  pressare  reyutator. 

Dr  Erroanct ytass  poppet  va/ve. 


11 


Sample  Calculations 

Since  only  temperature  differences  are  required  it  is  not  neces- 
sary to  make  temperature  corrections  for  stem  exposures. 


a Tw  _ L x (Tw)3 

AT  Lw  rT  T 


Baker’s  Purified  Stearic  Acid 


T 


P 


Tw 


267.7 

248,3 

19.4 


83  47 . 9 

38  33.2 

14.7 


ATw  = 14.7 

AT'  19.4 


0.758  = slope  of  Tw  - T curve 


Tw)3 


(47.9  + 273. I)3  - 1 

(267.7  + 273 .lT  2.84 


Lw 

1 

77.6 


x 


lw  x 18  where  1 = heat  of  vaporization 

of  water  per  gram 

0.758  x 569.7  x 18  x 2.84 
284.4 


= 139.6  B.t.u.  per 

5 


= 77,6  calories 

per  gram 

pound • 


TABLE  I 

12 

Baker’s  Stearic 

Acid 

1st  Determination 

2nd 

Determination 

v 

© 

© 

£ xj 

Jh  *a 

O CCS 

Cl 

O cJ 

£ 

a £ 

i 

•H  © 

a.  .a 

i 

T-I  © 

cd  &0 

•H 

■d 

a!  bO 

•H! 

»d 

> *H 

iH  £ 

© cd 

r-‘  & 

© cd 

-P 

rH  p 

1m 

+3 

r-3  £ 

<H  £ 

•H  O 

3 to 

<H  £ 

•H  O 

P bO 

O © 

-P  «H 

O © 

a a 

•P  *H 

O 

© 

cd  -P 

© 

© 

cd  -p 

© 

£ S 

lb  CJ 

© 

£ & 

1m  £ 

£ w 

•H 

© © 

£ © 

•H 

© © 

£ © 

(in 

a o 

B © 

<H 

a o 

-p  © 

© O 

a 

-p  © 

© O 

a 

crt  £ 

h 

© w 

d £ 

P 

® W 

£ bO 

p m 

-p  © 

£ bO 

p w 

-P  © 

© © 

m £ 

© 

© © 

w P 

© 

a-d 

m © 

a a 

a xi 

OT  © 

a £ 

a 

© -P 

© to 

a 

© -P 

© bo 

© £ 

£ © 

■p  © 

© c 

£ © 

-P  © 

EH  *H 

a a 

CO  XS 

Eh  *H 

a a 

CO  xS 

248.3 

38 

63 

250.0 

42 

57 

243.0 

250.7 

43 

248.3 

250.1 

42 

248.2 

250.3 

248.7 

250.0 

58 

248.1 

64 

250.5 

248.5 

250.4 

248.8 

250.2 

248.4 

250.8 

248.0 

63 

250.2 

62 

Av. 

248.3 

38 

63 

Av.250.3 

42 

59 

267.8 

83 

75 

269.0 

90 

60 

267.9 

269.1 

267.1 

269.5 

267.9 

269.7 

268.0 

76 

269.4 

61 

267.2 

269.6 

267.5 

269.8 

267.9 

269.4 

267.9 

269.3 

267.8 

77 

269.4 

63 

Av. 

267.7 

83 

76 

Av.269.4 

90 

61 

Sample 

of 

Purified 

Stearic  Acid 

obtained 

from  the 

Baker 

Chemical  Company 

T 


~f 


i •'  n 


TABLE  II 

13 

Commercial 

Stearic  Acid 

1st 

Determination 

2nd  Determination 

09 

09 

P 

P 

<D 

© 

© 

© 

P d 

-P 

p d 

-P 

O CCS 

© 

p 

O cd 

© 

P 

ft  p 

a 

•H  © 

ft  p 

a 

i-i  © 

Cd  fcO 

•H 

d 

cd  bO 

d 

K*  •H 

rH 

© CCJ 

t>  *rH 

i — \ 

© cd 

rH 

p p 

-P 

rH 

P P 

ft  p 

•H 

B bQ 

ft  P 

•H 

b 5b 

O <D 

B 

-P  *H 

o © 

B 

-P  iH 

O 

CCS  -P 

© 

cd  ft 

<D 

P 

P P 

© 

P 

P P 

in  09 

*H  l>j 

© © 

p © 

•H  }>s 

© © 

B © 

P 

ft  o 

B © 

P 

Ph  O 

■P  © 

© B 

a 

-p  © 

© B 

a 

Cd  P 

P O 

© 09 

cd  P 

P o 

© 09 

P h0 

B P 

•P  © 

P bO 

B P 

-P  © 

© © 

w © 

© 

© © 

09  © 

© 

ftd 

w a 

B & 

Ph  d 

09  a 

a p 

© 

© w 

a _ 

© 

© bO 

© p 

p ft 

-p  © 

© p 

p ft 

■P  © 

EH  iH 

PH  O 

co  d 

Eh  *H 

pH  o 

co  d 

241.9 

30 

64 

242.0 

28 

48 

242.1 

242.4 

242.4 

242.5 

242.5 

242.8 

243.1 

65 

242.5 

48 

242.5 

242.3 

242 . 9 

243.0 

242.6 

242.5 

242.4 

242.8 

242.5 

68 

242.3 

48 

kv .242 • 5 

30 

66 

Av.  242.4 

28 

48 

266.1 

80 

63 

271.5 

95 

65 

266.3 

272.5 

96 

266.6 

272.0 

95 

266.5 

272.6 

96 

266.8 

271.6 

95 

266.9 

81 

271.8 

95 

266.8 

81 

65 

272.1 

95 

65 

266.5 

80 

272.3 

95 

266.6 

271.8 

95 

266.3 

272.1 

95 

Av.266.5 

80 

64 

Av.  272.0 

95 

65 

Sample 

of  Commercial 

Stearic  Acid  obtained 

from 

Armour 1 

s Soap 

and  Glue  Works  of  Chicago, 

Illinois • 

\ 


< 


I 


vS 


\ 


TABLE  III 

14 

Commercial  Oleic  Acid 

1st 

Determination 

2nd 

Determination 

w 

ra 

Ph 

Ph 

0 

0 

0 

Ph  td 

+3 

Ph  »d 

■P 

c a 

0 

£ 

O cti 

0 

£ 

ft  ph 

g 

•H  0 

ft  Ph 

s 

•H  0 

ai  bQ 

•H 

•d 

d bQ 

♦H 

•d 

> .H 

rH 

0 CCS 

> *H 

• — i 

0 d 

+3 

r-i 

Pi  £ 

rH 

£ Ph 

CM  £ 

•H 

£ bQ 

Cm  £ 

•H 

3 bO 

O © 

g 

+3  *H 

O 0 

g 

43  »H 

o 

d -P 

O 

aJ  43 

0 

£ 

P-1  £ 

0 

£ 

Ph  £ 

Ph  w 

•H  !>s 

0 0 

Ph  CO 

•fH 

0 0 

p 0 

Ph 

ft  o 

£ 0 

Ph 

ft  o 

-p  0 

0 £ 

£ 

-P  0 

0 £ 

B 

0)  Ph 

P-i  o 

0 w 

aS  Ph 

Ph  O 

0 w 

Ph  bQ 

£ £ 

-p  0 

Ph  bO 

P Ph 

-p  0 

0 0 

GO  0 

0 

© 0 

OQ  0 

_ 0 

ft^ 

w g 

g pH 

ftt) 

W £ 

B Ph 

£ 

0 

0 bQ 

£ _ 

0 

0 bO 

0 £ 

£ <M 

-P  0 

0 £ 

Ph  <H 

-P  0 

E4  *H 

a*  o 

co  *d 

E4  *H 

Ph  O 

CO  n£ 

249.0 

62 

56 

246.6 

52 

43 

249.1 

246.7 

249.2 

247.0 

249.4 

57 

246.9 

249.2 

246.7 

46 

249.5 

246.7 

249.3 

58 

246.5 

249.0 

246.3 

249.2 

246.5 

249.4 

58 

246.6 

44 

A v. 

249.2 

62 

57 

Av.  246.7 

52 

44 

260.? 

98 

60 

264.5 

107 

41 

260.9 

264.4 

261.0 

264.6 

261.0 

264.8 

43 

260.9 

65 

265.1 

260.7 

264.9 

260.8 

264.7 

44 

261.0 

265.0 

261.0 

264.9 

260.9 

63 

264.8 

44 

Av. 

260.9 

98 

63 

Av.  264.8 

107 

43 

Sample 

of  Commercial 

Oleic 

Acid  obtained  from 

Armour 1 s 

Soap  and  Glue 

Works 

of  Chicago, 

Illinois 

• 

TABLE  IV 

15 

Baker’s  Oleic  Acid 

1st 

De  terrainati  on 

2nd 

Determination 

CO 

CO 

G 

0 

0 

0 

0 

G tJ 

-P 

G rd 

ft 

o cd 

0 

P 

O cd 

0 

P 

ft  G 

s 

•H  0 

ft  G 

s 

ft  0 

a!  t)0 

•r-J 

cd  hO 

ft 

ro 

> ft 

i — i 

0 cd 

> ft 

ft 

0 cd 

ft 

i-) 

G G 

JO 

ft 

G G 

ft  p 

ft 

p b0 

fti  P 

ft 

p qO 

o 0 

& 

ft  ft 

O 0 

G 

ft  ft 

o 

cd  ft 

O 

cd  ft 

0 

P 

G P 

0 

G 

G P 

G co 

•H  i>5 

0 0 

G “ 

ft  E-s 

0 0 

P 0 

G 

ft  O 

P 0 

G 

a o 

ft  0 

0 P 

s 

ft  0 

0 p 

a ! 

G o 

0 K 

Cd  G 

G o 

© CO 

G HQ 

P G 

-P  0 

G b3 

P G 

ft  0 

0 0 

CO  0 

0 

0 0 

co  0 

0 

ftrd 

ra  S 

S G 

ftdi 

W S 

a g 

S 

0 

0 tiO 

rj 

& 

0 

© oO 

0 P 

G ft 

ft  0 

0 P 

G ft 

ft  © 

EH  ft 

ft  o 

CO  rp 

E-t  ft 

ft  o 

co 'd 

252.8 

57 

60 

248.8 

48 

41 

252.7 

249.0 

252.8 

249.1 

253.0 

248.9 

253.1 

249.0 

39 

252.8 

249.2 

252.7 

248.9 

252.7 

249.0 

252.6 

65 

248.8 

42 

Av. 

252.8 

57 

63 

Av.  249.0 

48 

41 

268.6 

106 

60 

268.7 

107 

34 

268.6 

268.9 

268.7 

269.0 

268.7 

60 

269.0 

37 

268.8 

269.1 

268.7 

269.0 

268.7 

61 

269.1 

37 

268.7 

268.9 

268.8 

268.8 

268.7 

61 

269.0 

35 

Av. 

268.7 

106 

61 

Av.  269.0 

107 

36 

Sample 

of  U.  S. 

P.  Oleic  Acid  obtained  from 

Baker 

Chemical  Company 

TABLE  V 

16 

Double 

Distilled 

Garbage  Grease  Fatty 

Acids . 

1st 

Determination 

2nd 

Determination 

CO 

CO 

P 

p 

0 

© 

© 

0 

p •£> 

p 

P 

p 

O crf 

© 

p 

O crf 

© 

p 

Ph  P 

g 

•H  0 

Ph  P 

a 

♦H  © 

Crf  W 

•H 

•0 

crf  tafl 

ti 

r-i 

0 Crf 

*H 

r—i 

0 crf 

P 

rH 

P P 

P 

rH 

P P 

«H  P 

•H 

p t»D 

U P 

•H 

p bQ 

O 0 

a 

P *H 

O 0 

a 

p »H 

O 

Crf  P 

O 

Crf  P 

<D 

p 

P P 

0 

p 

P P 

P CO 

•H  {>5 

0 0 

p CO 

«H  >5 

0 0 

P CD 

P 

Ph  O 

p 0 

p 

Ph  O 

P 0 

© P 

s 

p 0 

0 p 

S 

Crf  P 

P ° 

0 M 

crf  p 

P O 

0 CO 

P bO 

P P 

P 0 

P bO 

P P 

P 0 

0 © 

W 0 

0 

© 0 

C0  0 

0 

Pi*© 

co  S 

E P 

P.1© 

co  a 

s h 

a 

0 

© QO 

S ^ 

0 

0 bO 

© c 

P Ch 

P © 

0 P 

p <p 

P 0 

Ph  O 

CO  no 

gH  *H 

Ph  O 

co  *d 

243.5 

38 

61 

241.7 

33 

69 

243.7 

38 

242.1 

243.7 

38 

241.9 

244.4 

39 

64 

242.0 

72 

244.2 

39 

241.8 

243.9 

38 

241.9 

243.8 

62 

242.2 

71 

243.9 

241.8 

243.9 

242.5 

243.9 

61 

242.3 

73 

Av. 

243.9 

38 

62 

Av.  242.0 

33 

71  " 

263.0 

82 

75 

269.8 

101 

78 

263.3 

270.1 

263.3 

270.3 

263.0 

77 

270.4 

83 

263.3 

270.7 

262.9 

270.6 

263.1 

74 

270.7 

76 

263.3 

270.6 

263.1 

270.3 

263.1 

76 

270.3 

78 

Av. 

263.1 

82 

75 

Av. 270.4 

101 

79 

Sample 

0f  Double 

Distilled  Garbage  Grease 

Patty 

Acids  obtained 

From  Armour 1 s Soap 

and 

Glue  Works  of 

Chicago,  Illinois. 

TABLE  VI 


17 


Double  Distilled 
1st  Determination 


© 

CQ 

g 

© 

G T5 

p 

G 

O erf 

© 

ft  G 

a 

•H  © 

erf  b0 

•H 

^ *r\ 

< — 1 

© Crf 

p 
ft  G 

H 

•H 

5 & 

0 <D 

a 

P «H 

0 

erf  P 

© 

g 

G G 

G w 

•H  r’S 

© © 

3 © 

in 

ft  O 

p © 

© 3 

a 

Oj  G 

G So 

G O 

© CO 

3 G 

-p  © 

© © 

CO  © 

© 

ftrp 

co  a 

a ht 

a 

© 

© bO 

© g 

G ft 

p © 

EH  *H 

ft  0 

to  rO 

247.9 

49 

65 

248.1 

248.2 

248.3 
248.5 
248.2 
248.2 
248.2 
248.2 
248.2 

67 

248.2 

49 

66 

264.2 

94 

70 

264.4 

264.3 

264.5 

265.0 

95 

265.8 

94 

264.9 

70 

264.7 

264.9 

264.7 

264.7 

94 

70 

Sample  of  Double 


Grease  Fatty  Acids 

2nd  Determination 


CO 

g 


© 

© 

G fp 

p 

O erf 

© 

G 

ft  G 

a 

•H  © 

orf  bO 

•H 

'P 

> *H 

rH 

© erf 

JO 

1 2 

G G 

ft  G 

•H 

p bO 

O © 

a 

P p 

0 

erf  P 

© 

G ^ 

G G 

G © 

•H  ^5 

© © 

3 © 

G 

ft  0 

P © 

© 3 

a 

erf  G 

G O 

© w 

G SO 

3 G 

p © 

© © 

© © 

^ © 

ftt^ 

© a 

fa  G 

a 

© 

© bO 

© G 

G ft 

P © 

EH  iH 

ft  0 

CO  np 

249.0 

50 

65 

248.6 

248.5 

248.9 

249.0 

248.7 

249.0 

248.8 

248.7 

248.8 

60 

•.  248.8 

50 

63 

266‘.4 

98 

74 

266.2 

97 

266.1 

266.2 

265.8 

266.0 

77 

266.3 
266.5 

266.4 
266.1 

75 

. 266.2 

97 

~76~ 

Brown  Grease 


Fatty  Acids  obtained  from  Armour’s  Soap 
and  Glue  Works  of  Chicago,  Illinois 


) 


1 ~f 


) 


* 


TABLE  VII 

18 

Double  Distilled  Coconut  Oil  Fatty  Acids 

1st 

Determination 

2nd 

Determination 

Temperature  of  vapor 
in  degrees  centigrade 

Pressure  in  millimeters 
of  mercury 

Stem  temperature  in 
degrees  centigrade 

Temperature  of  vapor 
in  degrees  centigrade 

Pressxire  in  millimeters 
of  mercury 

Stem  temperature  in 
degrees  centigrade 

212.0 

64 

63 

208.5 

62 

45 

212.7 

66 

209.0 

215.1 

67 

208.9 

213.2 

67 

64 

209.3 

43 

213.0 

209.1 

213.4 

209.0 

213.3 

66 

209.5 

40 

213.0 

209.3 

213.0 

209.0 

213.0 

66 

208.5 

40 

Av. 

213.0 

67 

65 

Av.  209.0 

62 

42 

223.6 

110 

64 

225.0 

111 

74 

223.8 

110 

224.8 

111 

224.0 

110 

224.3 

110 

224.1 

61 

224.0 

73 

224.0 

224.5 

224.2 

224.4 

224.3 

61 

224.6 

72 

224.0 

224.3 

223.9 

224.4 

224.0 

61 

224.7 

73 

Av. 

224.0 

110 

62 

Av.  224.5 

110 

73 

Sample 

of  Double  Distilled  Coconut 

Oil 

Fatty 

Acids 

obtained  from  Armour*  i 

3 

Soap  and 

Glue 

works  of  Chicago,  Illinois. 

J 


' 


. 


■ 


TABLE  VIII 


19 


Double  Distilled  Neats  Foot  Oil  Fatty  Acids 


1st  Determination 


2nd  Determination 


© 

03 

Sh 

© 

Sh  •£ 

ft 

O erf 

© 

2 

ft  Sh 

a 

ft  © 

erf  to 

♦h 

'd 

t>  «H 

i — i 

© erf 

ft 

ft 

g a 

ft  £ 

•H 

2 to 

o © 

a 

ft  ft 

o 

erf  ft 

© 

£ 

Sh  £ 

Sh  03 

ft  >s 

© © 

£ © 

G 

2.  o 

ft  © 

© 2 

a 

erf  Sh 

Sh  O 

<D  co 

Sh  tO 

3 G 

ft  © 

© © 

CO  (D 

© 

ft*d 

co  a 

a a 

a 

© 

© to 

© Sh 

2 ft 

ft  © 

ft  ft 

ft  o 

co 'd 

242.5 

39 

60 

242.8 

243.0 

243.2 

243.2 

243.0 

243.1 

243.3 
243.0 
243.0 


63 


65 


Av. 

243.0 

39 

63 

264.4 

264.6 

93 

68 

264.7 

264.7 

264.3 

70 

264.7 

264.5 

72 

264.6 

264.7 

264.8 

70 

Av. 

264.6 

93 

70 

<D 
Sh  'O 
O erf 
ft  Sh 
erf  taO 
t>  ft 
ft 
ft  £ 
O © 
O 


<D 
U 
2 
ft 
erf 
Sh 
CD  © 
PhTS 


CO 

© 

© 

Sh 


© £ 
ft  ft 


co 

G 

© 

ft 

© 

5 

ft 

ft 

ft 

a 

ft  f>5 

© 3 

CO  © 
CO  g 
© 

Sh  ft 
ft  O 


£ 

ft  © 
•G 
© erf 

a 

G qO 

ft  ft 
erf  ft 
Sh  £ 
© © 
ft  O 

a 

© CO 
ft  © 
© 

£ h 

© to 
ft  © 
m *d 


242.5 

38 

49 

242.7 

38 

243.1 

39 

243.1 

39 

51 

243.1 

39 

242.7 

38 

243.2 

39 

50 

242.8 

39 

243.5 

41 

243.5 

41 

51 

. 243.0 

39 

50 

262.8 

87 

59 

263.0 

88 

263.3 

89 

263.0 

88 

262.8 

87 

60 

263.2 

88 

263.2 

88 

263.0 

263.0 

263  • 0 

61 

. 263.0 

88 

60 

Sample  of  Double  Distilled  Neats  Foot  Oil 
Fatty  Acids  obtained  from  Armour’s  Soap 
and  Glue  Works  of  Chicago,  Illinois 


TABLE  IX 

20 

Twitchellized 

Soya  Bean 

Oil  Fatty  Acids 

1st 

Determination 

2nd 

Determination 

Temperature  of  vapor 
in  degrees  centigrade 

Pressure  in  millimeters 
of  mercury 

Stem  temperature  in 
degrees  centigrade 

Temperature  of  vapor 
in  degrees  centigrade 

Pressure  in  millimeters 
of  mercury 

Stem  temperature  in 
degrees  centigrade 

248.8 

35 

62 

252.2 

43 

50 

249.0 

35 

252.3 

249.4 

36 

252.4 

250.3 

37 

64 

252.7 

250.8 

37 

253.0 

249.5 

36 

252.6 

249.5 

36 

65 

252.4 

249.2 

36 

252.3 

249.2 

36 

252.8 

249.0 

35 

63 

252.5 

55 

Av. 

249.5 

36 

64 

Av.  252.5 

53 

270.0 

82 

75 

271.0 

88 

51 

270.2 

271.2 

88 

269.8 

271.0 

88 

269.9 

271.8 

89 

270.0 

271.5 

89 

270.4 

271.5 

89 

270.2 

75 

272.0 

89 

269.8 

272.2 

90 

270.0 

271.7 

90 

270.0 

271.5 

89 

60 

Av. 

270.0 

82 

75 

Av.  271.5 

89 

59 

Sample  of  Twitchellized  Soya  Bean 

Oil 

Patty  Acids  obtained 

from  Armour 

's 

Soap 

and  Glue 

Works  of  Chicago,  Illinois 

TABLE  X 

21 

Double  Distilled  Corn 

Oil  Fatty  Acids 

1st 

Determination 

2nd 

Determination 

Temperature  of  vapor 
in  degrees  centigrade 

03 

<D 

■P 

<D 

e 

•H 

r-' 
r— ‘ 

•H 

a 

5 
© h 
UZ 

w ® 
co  a 
<s> 

^ o 

Stem  temperature  in 
degrees  centigrade 

Temperature  of  vapor 
in  degrees  centigrade 

to 

u 

<D 

-P 

0> 

p 

•H 

r—l 

•H 

3 

£ 

•r-!  >s 

<D  ?! 
M O 

3 

02  <D 
CO  £ 
<D 

tu  o 

Stem  temperature  in 
degrees  centigrade 

242.2 

38 

48 

239.5 

31 

63 

242.7 

239.3 

242.8 

239.5 

242.5 

239.7 

59 

242.2 

239.3 

242.8 

239.6 

242.5 

239.3 

242.3 

239.5 

242.4 

239.8 

242.7 

239.6 

61 

Av. 

242.5" 

38 

48 

Av.  239.5 

31 

61 

264.5 

90 

62 

268.3 

102 

80 

264.0 

89 

268.5 

264.2 

90 

269.0 

264.4 

268.9 

78 

264.5 

269.2 

264.7 

70 

269.0 

265.2 

91 

268.8 

77 

264.8 

90 

268.6 

264.5 

269.0 

264.3 

68 

268.8 

76 

Av. 

264.5 

90 

67 

268.8 

102 

78 

Sample  of  Double  Distilled  Corn  Oil 

Fatty 

Acids 

obtained 

from  Armour ' s Soap  and  Glue 

Works  of 

Chicago, 

Illinois • 

TABLE  XI  22 

Double  Distilled  Cotton  Seed  Oil 
1st  Determination  2nd  Determination 


m 

P 

co 

P 

0 

00 

si 

CD 

CD 

P nO 

p 

P ’Xj 

P 

d 

o d 

<D 

♦H 

O Cd 

00 

•H 

ft  p 

a 

CD 

ft  p 

a 

0 

cd  bO 

•H 

co  nO 

cd  bd 

•H 

co  nl 

> *H 

rH 

cd 

> ft 

iH 

0 cd 

ft 

i — i 

P P 

P 

rH 

P P 

ft  £ 

•H 

2 bO 

ft  Si 

•H 

3 bO 

O <D 

a 

ft  ft 

O (D 

a 

ft  ft 

O 

cd  ft 

O 

cd  P 

<D 

S3 

P si 

CD 

p 

p d 

P CO 

•H  t>s 

CD  CD 

P CO 

ft  >5 

0 00 

P 0 

P 

ft  o 

P CD 

p 

ft  o 

ft  0 

CD  £ 

a 

P CD 

00  2 

a 

05  P 

P O 

00  CO 

P P 

P o 

0 co 

P bQ 

d p 

P 0 

P bO 

3 p 

p 0 

0 <D 

CO  0 

CD 

CD  CD 

CO  0 

0 

ftnO 

w a 

a k 

ft'P 

co  a 

a p 

a 

CD 

00  oO 

a 

0 

0 bO 

<D  Si 

P ft 

P CD 

CD  £ 

p ft 

P 0 

Eh  «H 

ft  o 

co  ms 

EH  ft 

ft  o 

co  *d 

254.8 

47 

65 

251.8 

47 

60 

255.0 

50 

252.3 

255.1 

50 

252.0 

255.1 

65 

251.5 

255.3 

251.6 

255.1 

251.6 

60 

255.2 

64 

252.0 

255.0 

252.1 

255.1 

252.0 

255.1 

65 

251.5 

61 

Av. 

255.1 

50 

65 

Av. 

251.8 

47 

60 

272.1 

101 

76 

271.3 

99 

65 

272.2 

271.1 

272.4 

271.2 

272.5 

271.1 

272.5 

75 

271.4 

272.5 

271.4 

272.7 

271.6 

272.7 

271.8 

272.7 

71 

271.9 

272.5 

271.5 

Av. 

~27§TF~” 

101 

74 

Av. 

271.4 

99 

65 

Sample  of  Double  Distilled  Cotton  Seed 
Oil  Fatty  Acids  obtained  from  Armour’s 
Soap  and  Glue  Works  of  Chicago,  Illinois* 


TABULATED  RESULTS. 

1st  Determination 

l 

Slope  Heat  of  Vaporization  Heat  of  Vaporization 
A Tw  cal./gm.  B.t.u./lb 


AH 

Baker’s  Stearic 
Acid 

0.758 

77.6 

139.6 

Commercial  Stearie 
Acid 

0.758 

78.5 

141.3 

Baker’s  Cleic 
Acid 

0.768 

76.8 

138.3 

Commercial  Oleic 
Acid 

0.769 

78.2 

140.7 

Double  Distilled 
Garbage  Grease 
Patty  Acids 

0.750 

78.3 

140.9 

Double  Distilled 
Brown  Grease 
Patty  Acids 

0.764 

78.5 

141.3 

Double  Distilled 
Coconut  Oil 
Fatty  Acids 

0.754 

85.8 

154.5 

Double  Distilled 
Neats  Foot  Oil 
Patty  Acids 

0.764 

78.5 

141.4 

Twitcliellized 
Soya  Bean  Oil 
Fatty  Acids 

0.746 

79.8 

143.6 

Double  Distilled 
Corn  Oil  Patty 
Acids 

0.741 

76.8 

137.8 

Double  Distilled 
Cottonseed  Oil 
Patty  Acids 

0.782 

81.8 

147.5 

23a 


TABULATED  RESULTS. 

2nd  Determination 


Slope 

Heat  of  Vaporization  Heat 

of  Vapori: 

A Tw 
A T 

cal./gra. 

B. b . u . / lb 

Baker* s Stearic 
Acid 

0.759 

77.2 

139.6 

Commercial  Stearic 
Acid 

0.770 

78.6 

141.4 

Baker’s  Oleic 
Acid 

0.780 

77.8 

140.0 

Commercial  Oleic 
Acid 

0.779 

76.4 

137.6 

Double  Distilled 
Garbage  Grease 
Fatty  Acids 

0.743 

78.1 

140.7 

Double  Distilled 
Brown  Grease 
Fatty  Acids 

0.736 

75.6 

136.1 

Double  Distilled 
Coconut  Oil 
Fatty  Acids 

0.744 

83.9 

150.9 

Double  Distilled 
Neats  Foot  Oil 
Fatty  Acids 

0.765 

79.0 

142.1 

Twitchellized 
Soya  Bean  Oil 
Fatty  Acids 

0.742 

78.8 

141.9 

Double  Distilled 
Corn  Oil  Fatty 
Ac  ids 

0.746 

78.8 

141.8 

Double  Distilled 
Cottonseed  Oil 

Fatty  Acids 

0.745 

78.0 

140.3 

24 


V.  SUMMARY  • 

(1)  In  the  design,  development,  and  calculation  of  the  cost  of 
operation  of  fatty  acid  distillation  plants  one  of  the  important 
factors  is  the  latent  heat  of  vaporization  of  these  acids.  Very  few 
of  these  values  have  been  reported  and  in  all  cases  the  agreement 

is  poor. 

(2)  Calorimetric  determinations  of  the  heats  of  vaporization 
of  these  fatty  acids  could  not  be  accepted  as  even  an  approximation 
of  the  correct  values  due  to  the  early  condensation  in  the  delivery 
tube  and  the  conduction  of  heat  to  the  calorimeter  from  the  still. 

In  the  case  of  mixtures  the  per  cent  of  the  lighter  fraction  would 
probably  be  higher  in  the  distillate  and  result  in  fictious  values. 

(3)  The  method  of  determining  the  heat  of  vaporization  by  means 
of  the  vapor  pressure  curves  and  the  Clapeyron  relation  is  easy  to 
carry  out  and  is  fairly  accurate.  The  boiling  points  reported  may 
be  considered  to  be  the  mean  boiling  points  of  the  samples  in  ques- 
tion, but  would  undoubtedly  be  different  for  nearly  every  other 
sample  that  might  be  tested  due  to  some  variation  in  composition. 
Decomposition  goes  on  as  the  acids  are  heated  which  causes  a slo w 
but  gradual  increase  in  the  boiling  points. 

(4)  The  greatest  discrepancy  between  duplicated  samples  is 

5 per  cent.  Y/ith  the  exception  of  coconut  oil  the  heat  of  vaporiza- 
tion of  the  fatty  acids  may  be  taken  as  y'8  calories  per  gram  or 
S40  B.t.u.  per  pound.  The  values  reported  can  be  nothing  more 
than  approximations  but  may  be  considered  to  be  sufficiently  ac- 
curate  for  industrial  purposes . 


25 


VI.  BIBLIOGRAPHY 


1.  J.  Ind.  and  Eng.  Chem.,  vol.12,  490  (1920). 

2.  J.  Am.  Chem.  Soc.,  vol.33,  pp. 863-888  (1911). 

3.  J.  Ind.  and  Eng.  Chem.,  vol.14,  486  (1922). 

4.  Zeit.  physik.  Chem . 62 , 336  (1908). 

Lewkowitsch-Warburton.  "Chemical  Technology  and  Analysis 

of  Oils,  Fats,  and  Waxes."  6th  Edition.  Vol.II,  pp. 197, 652. 


